Method of eliminating blisters in a glass making process

ABSTRACT

A method of controlling blister formation in a glass melt flowing through a system comprising one ore more refractory metal vessels by developing a blister index and determining the critical blister index value. The critical value of the blister index may be used to control the principal variables responsible for blister formation, including the water content of the melt, the concentration of reduced multivalent oxide compounds in the melt, and the hydrogen partial pressure of an atmosphere in contact with the outside surface of the refractory metal vessel. Also disclosed is a minimum partial pressure of hydrogen necessary to produce an essentially blister-free glass article in a glass essentially free of arsenic and antimony.

This application claims the benefit of priority under 35 U.S.C. § 119(e)of U.S. Provisional Application Ser. No. 60/749,024 filed on Dec. 8,2005, the content of which is incorporated herein in its entirety byreference.

BACKGROUND OF THE INVENTION FIELD OF THE INVENTION

This invention is directed to a method of forming glasses withoutblisters in manufacturing processes containing refractory metal systems,and in particular, refractory metal conditioning systems. The inventionis particularly useful for, but not limited to, forming high melting orhigh strain point glasses, such as are used for glass substrates forflat panel display devices, and glasses which are essentially arsenic orantimony-free, in manufacturing processes utilizing refractory metals,such as platinum or platinum alloys, which contact the glass.

TECHNICAL BACKGROUND

Manufacture of hard alumino-borosilicate glass, e.g. for flat paneldisplays, requires low levels of gaseous inclusions (blisters).Advantageously, refractory metal conditioning systems may be used toavoid refractory outgassing in the final stages of melting, where anyblister formed will become a defect. Such refractory metal systems(typically Pt or Pt—Rh alloys) are generally considered to be inert inrelation to most glasses, and thus not cause any inclusions in the finalglass product. However, this is not necessarily valid. Reactions thatoccur at the metal/glass interface inside the vessels lead to thegeneration of gaseous inclusion within the glass melt and thus the finalglass product (e.g. glass sheet).

One of the more common reactions that occur at the metal/glass interfaceis the conversion of negatively charged oxygen ions to molecular oxygenwhich is caused by the thermal breakdown of water and hydroxyl (OH)species in the glass melt. This phenomenon occurs because at theelevated temperatures of glass melting and delivery, a low partialpressure of hydrogen exists in the glass melt. When hydrogen in theglass melt comes in contact with the refractory metal vessel, thehydrogen rapidly permeates out of the vessel and into the atmosphereoutside the vessel, depleting the refractory metal/glass interfacialregion of the glass melt of hydrogen. Thus, the permeation of hydrogenfrom within the vessel, through the vessel wall(s) into the atmosphereoutside of the vessel increases the free oxygen within the molten glass(glass melt). Thus, in the breakdown of water, for example, for everytwo moles of hydrogen that leaves the glass melt due to permeation, amole of oxygen is left behind at the metal/glass interfacial region ofthe melt. As the hydrogen leaves the glass melt, the oxygen (or thepartial pressure of oxygen) increases, leading to the generation ofblisters or gaseous inclusions within the melt.

The hydrogen permeation rate through the walls of the refractory metalvessel, and, therefore, the generation rate of neutral molecular oxygenat the refractory metal/glass melt interface, is proportional to thedifference between the square roots of the external and internalhydrogen partial pressures.

Additionally, there are other reactions which involve the catalyzing oroxidation of other species in the glass melt, such as halogens (Cl, F,Br), that can lead to the generation of gaseous inclusions. Further,electrochemical reactions can occur at the metal/glass interface. Theseelectrochemical reactions can be associated with thermal cells, galvaniccells, high AC or DC current applications and grounding situations.

For some applications, blisters in the glass drawn from the glassmanufacturing system may pose little problem, and may, under somecircumstances, provide aesthetic value. However, in the manufacture ofglass substrates for use in the manufacture of flat panel displaydevices such as liquid crystal displays (LCD) and organic light emittingdiode (OLED) displays, blistering makes the resultant glass substrate(sheet) unusable. Therefore, there is tremendous advantage to a processwhich mitigates against the presence of gaseous inclusions.

Today, there are several known methods that can be used to address theforegoing reactions which cause the formation of blisters in the glassmelt. One known method that can be used to help minimize the formationof gaseous inclusions in the finished glass product involves the use offining agents in the glass melting and conditioning stages. Finingagents are multivalent oxygen-containing compounds that release orabsorb oxygen based on temperature.

Arsenic is among the highest temperature fining agents known, and, whenadded to the molten glass batch material, it allows for O₂ release(reduction) from the glass melt at high melting temperatures (e.g. above1450° C.). This high temperature O₂ release, which aids in the removalof gaseous inclusions during the melting and fining stages of glassproduction results in a glass product (e.g. glass sheet), that isessentially free of gaseous inclusions. Furthermore, any residual oxygenis reabsorbed by the fining agent during the transition from a reducedstate to an oxidized state as the glass cools.

Unfortunately, from an environmental point of view, arsenic isconsidered a hazardous material, and therefore undesirable as a finingagent. Other, less effective fining agents are available, such asantimony and tin, but antimony is also environmentally undesirable, andtin much less effective than either arsenic or antimony.

The need to eliminate environmentally unfavorable but effective finingagents, such as arsenic and antimony, in order to remove gaseousinclusions in the glass melt has required the use of less effectivefining agents, and placed greater emphasis on addressing the generationof gaseous inclusions.

There are other methods available to mitigate reactions that lead to theformation of gaseous inclusions in the glass. U.S. Pat. No. 5,785,726,for example, discloses a humidity controlled enclosure that surroundsone or more platinum-containing vessels and is used to control thepartial pressure of hydrogen outside the vessel(s) so as to reduce theformation of gaseous inclusions. The breakdown of the water in themoisture-laden atmosphere within the enclosure produces hydrogen whichin turn helps to suppress the aforementioned hydrogen permeation.Although the enclosure described in U.S. Pat. No. 5,785,726 successfullyreduces the formation of gaseous inclusions, it has several drawbacks.First, the enclosure is so large that it makes it difficult if notimpossible to maintain a uniform environment around theplatinum-containing components of the glass making apparatus. Second,the environment within the enclosure is so hot and humid that it can beuncomfortable to people that must work within the enclosure. U.S. patentapplication Ser. No. 11/116,669 improved upon the traditional enclosuredescribed in U.S. Pat. No. 5,785,726, disclosing encapsulating therefractory metal components of a glass making apparatus within arelatively tight fitting enclosure (capsule). Use of a capsule allowsimproved control of the atmosphere within the relatively small volumebetween the capsule and the encapsulated glass-carrying refractory metalcomponents. This is due to the fact that a probe reading (such asrelative humidity or dew point temperature) for conditions inside thecapsule is more likely to be representative of conditions at theexterior surfaces of the refractory metal glass processing equipmentthan measurements taken within the large volume of space within theprior large, room-sized enclosure. Additionally, if there is a processinstability or change in the water content of the molten glass withinthe refractory metal vessel(s) that leads to an increase in hydrogenpermeation blistering, then there is often no way to respond to thisproblem using the conventional enclosure disclosed in U.S. Pat. No.5,785,726 since it may be operating at its maximum dew point. Moreover,response time of the capsule of U.S. patent application Ser. No.11/116,669 to process instabilities is greatly enhanced owing to thesmall volume contained between the capsule and the refractory metalvessel(s) compared to the conventional enclosure. That is, the changesin the humidity (dew point) within the capsule volume, and therefore thehydrogen partial pressure, can be performed much more rapidly than wouldbe possible in a room-sized enclosure.

Nevertheless, in spite of the improvements in hydrogen permeationblister control represented by the methods described above, they arebased entirely on the water content of the glass, and control of themoisture content of the atmosphere surrounding the refractory metalvessels comprising the glass manufacturing apparatus. Moreover, thesemethods have to date been empirical in nature, and therefore appliedwith a large dose of guesswork with regard to the partial pressure ofhydrogen necessary to suppress blister formation. It would be beneficialif hydrogen permeation blistering control could be undertaken with amore complete understanding of the impact of other blistering factors,such as the total concentration of multivalent oxygen-containingcompounds within the glass. This has become particularly important as,for environmental reasons; the total concentration of multivalentcompounds introduced into the glass batch has been decreased.

SUMMARY

In one broad aspect of the present invention, a method of making a glassarticle is disclosed comprising flowing a molten glass at a temperatureof at least about 1550° C. in a vessel comprising a refractory metalwall having an inside surface in contact with the molten glass, andwherein a partial pressure of hydrogen at an outside surface of therefractory metal wall is at least about 10^(—6) bar, forming the moltenglass into the glass article, and wherein the glass article comprises atotal concentration of reduced multivalent compounds equal to or lessthan about 0.04 mole % and a β_(OH) of at least about 0.4 mm⁻¹.

According to another embodiment, a method of making a glass article ispresented comprising flowing a molten glass at a temperature of at leastabout 1550° C. in a vessel comprising a refractory metal wall having aninside surface in contact with the molten glass, and wherein a partialpressure of hydrogen at an outside surface of the refractory metal wallis at least about 10⁻⁶ bar; forming the molten glass into the glassarticle, and wherein the glass article comprises a β_(OH) of at leastabout 0.4 mm⁻¹, a total concentration of SnO and SnO2 less than or equalto 0.112 mole %, and a total concentration in the glass article of allother multivalent compounds not comprising tin is less than or equal toabout 0.04 mole %.

In accordance with still another broad aspect of the invention, a methodof making a glass article is disclosed comprising flowing a molten glassat a temperature of at least about 1550° C. in a vessel comprising arefractory metal wall having an inside surface in contact with themolten glass, and wherein a partial pressure of hydrogen (pH₂) in bar atan outside surface of the refractory metal wall is greater than or equalto an amount calculated according to the expression pH₂=2.39×10⁻⁴β_(OH)²−1.81×10⁻⁴β_(OH)+3.52×10⁻⁵ bar, forming the molten glass into the glassarticle; and wherein the glass article comprises a β_(OH) of at leastabout 0.4 mm⁻¹ and a total of no more than about 0.04 mole % of reducedmultivalent compounds.

In yet another embodiment according to the present invention, a methodof making a glass article is described comprising melting a batchmaterial comprising a multivalent compound to form a glass melt, flowingthe glass melt through a refractory metal vessel, an atmosphere incontact with an outside surface of the refractory metal vesselcomprising a partial pressure of hydrogen pH₂, forming a glass articlefrom the glass melt, the glass article comprising a concentration of areduced multivalent oxide compound and a water content expressed asβ_(OH), calculating a blister index from the reduced multivalent oxidecompound concentration, the β_(OH) concentration and the partialpressure of hydrogen and maintaining the blister index below apredetermined value by controlling the multivalent oxide compound in thebatch material, the water content, or the partial pressure of hydrogen,or a combination thereof.

Also disclosed in a method of making a glass comprising flowing a moltenglass at a temperature of at least about 1550° C. in a vessel comprisinga platinum or platinum alloy wall having an inside surface in contactwith the molten glass, and wherein a partial pressure of hydrogen at anoutside surface of the platinum or platinum alloy wall is at least about10⁻⁶ bar, and wherein the resultant glass comprises a totalconcentration of reduced multivalent compounds equal to or less thanabout 0.04 mole %, a β_(OH) of at least about 0.4 mm⁻¹ and no more than0.2 gaseous inclusions per pound of glass.

Also disclosed is a glass sheet comprising a total tin content expressedas SnO₂ that is less than or equal to about 0.112 mole %, a totalarsenic content expressed as As₂O₃ that is less than or equal to about0.016 mole %, a total antimony content expressed as Sb₂O₃ that is lessthan or equal to 0.011 mole %, a total iron content expressed as Fe₂O₃that is less than or equal to about 0.037 mole % and wherein the glasssheet contains no more than about 0.2 gaseous inclusions per pound ofglass.

The invention will be understood more easily and other objects,characteristics, details and advantages thereof will become more clearlyapparent in the course of the following explanatory description, whichis given, without in any way implying a limitation, with reference tothe attached Figures. It is intended that all such additional systems,methods features and advantages be included within this description, bewithin the scope of the present invention, and be protected by theaccompanying claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view that shows the components of a glassmanufacturing system in accordance with an embodiment of the presentinvention.

FIG. 2 is an exemplary plot showing a correlation between the number ofblisters per pound of glass to the blister index.

FIG. 3 is an exemplary plot showing a curve denoting the minimum partialpressure of hydrogen as a function of β_(OH) in order to minimizegaseous inclusions in the glass.

DETAILED DESCRIPTION

In the following detailed description, for purposes of explanation andnot limitation, example embodiments disclosing specific details are setforth to provide a thorough understanding of the present invention.However, it will be apparent to one having ordinary skill in the art,having had the benefit of the present disclosure, that the presentinvention may be practiced in other embodiments that depart from thespecific details disclosed herein. Moreover, descriptions of well-knowndevices, methods and materials may be omitted so as not to obscure thedescription of the present invention. Finally, wherever applicable, likereference numerals refer to like elements.

The present invention relates to a method of melting and forming glassesin a manufacturing system containing glass-contacting metals. Metalsused to contact glass in a glass manufacturing system must be capable ofwithstanding the high melting temperatures of various glasses withoutstructural failure, while at the same time minimizing the release ofcontaminants into the glass by, for example, oxidation of the metal.Such metals are typically chosen from the platinum group, i.e. iridium,osmium, palladium, platinum, rhodium, and ruthenium, or alloys thereof,either with each other, or other metals, such as, for example,molybdenum, tin, antimony, silver, gold and iron. These high meltingtemperature metals and/or alloys will hereinafter be referred to asrefractory metals. The present invention is particularly beneficial for,but not limited to, the making of glass containing essentially noantimony or arsenic, i.e. essentially arsenic or antimony free.

While not wishing to be bound by theory, it is believed that theblistering effect which occurs in refractory metal vessels, such as aplatinum or platinum alloy fining vessel, for example, occurs as aresult of formation of an oxygen-rich layer of glass melt at therefractory metal-glass melt interface. This oxygen-rich layer in theglass is believed to be produced by a combination of thermoelectricelectrolysis of the melt, reduction of oxide fining agents (i.e.multivalent oxide compounds), and the number of hydroxyl (OH) groupsdissolved in the glass. The last effect is believed to have a largeimpact on the rate of blistering as a result of contact of the glasswith the refractory metal. It is believed that OH groups dissociate tosome extent into neutral hydrogen and oxygen. The hydrogen can thenpermeate through the refractory metal wall, enriching the interfaceregion (refractory metal-contacting region) of the glass with oxygenwhich can then form bubbles (seeds or blisters) if the oxygen solubilitylimit of the glass is exceeded. Thus, by controlling the relativepartial pressure of hydrogen outside the refractory metal system versusthat inside the refractory metal system, and more specifically, withinthe glass melt, hydrogen permeation through the refractory metal can becontrolled, thereby minimizing or eliminating blister formation.

Referring to FIG. 1, there is shown a schematic view of an exemplaryglass manufacturing system 100 that uses the fusion process to makeglass sheets 137 in accordance with the present invention. In the fusionprocess, a molten glass is flowed into a wedge shaped, open-topped pipe(often referred to as an isopipe). The glass overflows the pipe in twoseparate flows. The separate flows join, or fuse, at the lower apex ofthe wedge-shaped pipe to form a glass ribbon which is later cut intoindividual glass sheets. The fusion process finds considerable use inthe manufacture of glass substrates for the display glass industry.However, while a fusion process is shown, it will be appreciated thatthe present invention is useful anytime a molten glass is flowed throughor contained within a refractory metal vessel (e.g. platinum or aplatinum alloy) and has a low complement of multivalent ions, but forwhich a low concentration of blisters is desired. For example, a glassarticle may be formed using the well-known float process using theteachings of the present invention. Another suitable method of forming aglass article in accordance with the present invention is the so calledslot draw method.

The glass manufacturing system 100 includes a melting vessel 110 inwhich batch materials are introduced as shown by arrow 112 and thenmelted to form molten glass 114. The melting vessel 110 is typicallymade from a refractory material, typically a ceramic refractorymaterial. The glass manufacturing system 100 further includes componentsthat are made from a refractory metal, typically platinum or a platinumcontaining alloy such as Pt—Rh, Pt—Ir, etc. and combinations thereof.The refractory metal components include a melting tank (melter) to finerconnection tube 113, fining vessel 115 (e.g. finer tube 115), a mixingvessel 120 (e.g. stir chamber 120), a finer to stir chamber connectingtube 122, a delivery vessel 125 (e.g. bowl 125), a stir chamber to bowlconnecting tube 127, a downcorner 130 and an inlet 132. The inlet 132 iscoupled to forming vessel 135 (e.g. isopipe 135) which forms the glasssheet 137. Typically, the forming vessel 135, similar to the meltingtank, is made from a refractory material, and in particular a refractoryceramic material.

In one embodiment of the present invention, the melting/delivery system141, which includes vessels 115, 120, 125 and tubes 122, 127 and 130, isencapsulated or encased with a capsule 140. A jacket volume 142 isdefined between the interior walls of the capsule 140 and the exteriorwalls of components 115, 120, 122, 125, 127 and 130 in themelting/delivery system 141. The capsule 140 is preferably leak tight tothe extent that it may be used for maintaining a slightly more positivepressure of low oxygen, moist atmosphere inside the jacket volume 142that is greater than ambient conditions. As shown, capsule 140 can bemade as one zone which encloses the entire length of themelting/delivery system 141. Alternatively, multiple capsules 140 can beused as multiple zones where a plurality of individual capsules 140enclose one or more of the vessels 115, 120, 125 and tubes 122, 127 and130. An advantage of using multiple capsules 140 is the ability toindependently control the atmosphere in a particular area of themelting/delivery system 141.

The present invention may also include a closed-loop control system 144that controls the environment/atmosphere within capsule 140 and preventsthe aforementioned reactions from occurring at the refractorymetal/glass interface inside components 115, 120, 122, 125, 127 and 130.Again, the aforementioned reactions lead to the formation of gaseousinclusions in the glass sheet 137. In addition, the aforementionedreactions with the refractory metal vessels and tubes can lead tofailure of the refractory metal components 115, 120, 122, 125, 127 and130.

In particular, the closed loop control system 144 controls theatmosphere inside capsule 140 so as to suppress undesirable reactions atthe metal/glass interface by causing the migration of hydrogen fromoutside the refractory metal components into the glass/refractory metalinterface. A controlled level of hydrogen permeation into theglass/refractory metal interface reduces the production of undesirablespecies such as molecular oxygen, and halogens, within the glass whichin turn prevents the formation of undesirable gaseous inclusions in themolten glass 114. Hydrogen permeation into the glass/refractory metalinterface is achieved by supplying a higher partial pressure of hydrogento the exterior surfaces (non-glass contact surfaces of the refractorymetal vessel) in the mixing/delivery system 141, relative to theinterior glass/refractory metal interfaces. To accomplish this, a humid,low oxygen atmosphere that results in a controlled level of hydrogen atthe non-glass contact surface of the refractory metal system may bemaintained inside capsule 140. It should be noted that the hydrogenlevel in the atmosphere inside capsule 140 is undetectable. However,hydrogen is generated when water in the moisture-laden atmosphere breaksdown at the high temperatures associated with molten glass 114.

Alternatively, and more preferably, a hydrogen-containing gas may bedirectly employed to control the hydrogen partial pressure withincapsule 140. For example, a mixture of primarily nitrogen gas, with apercentage of hydrogen gas mixed in, could be pumped into the enclosure,the percentage of hydrogen being varied as needed. This later approachhas the advantage of a more direct determination of the amount ofhydrogen in the capsule atmosphere, and more precise control thereof.

The exemplary closed loop control system 144 includes a controller 150that obtains sensor readings from one or more sensor locations withinand outside capsule 140. These various sensors may be used to determinegas flow rates, gas concentrations, partial pressures and dew point, ifneeded, in order to control the partial pressure of hydrogen within thecapsule atmosphere. The controller 150 processes the sensor measurementsand controls different devices like gas or humidity feeds,heating/cooling controls, and so forth. As shown, controller 150 canobtain sensor readings from capsule supply sensors 152, capsule sensors154 and capsule exit sensors 156 and 156′. In this example, the capsulesupply sensors 152 include flow sensor 152 a, a dew point/humiditysensor 152 b, a temperature sensor 152 c, an oxygen sensor 152 d and apressure sensor 152 e. The capsule sensors 154 include a flow sensor 154a, a dew point/humidity sensor 154 b, a temperature sensor 154 c, anoxygen sensor 154 d and a pressure sensor 154 e. The capsule exitsensors 156 and 156′ each include a flow sensor 156 a and 156 a′, a dewpoint/humidity sensor 156 b and 156 b′, a temperature sensor 156 c and156 c′, and oxygen sensor 156 d and 156 d′, and a pressure sensor 156 eand 156 e′.

Controller 150 processes the sensor measurements and controls differentdevices like humidity feed system 158, heating/cooling control system160, air handler(s) 162 and O₂/N₂ makeup system 164. Air handler(s) 162have access to air and steam. All of the devices 158, 160, 162 and 164are connected to a network of pipes 166 which as shown is connected tocapsule 140. In operation, controller 150 controls devices 158, 160, 162and 164 to create an environment/atrnosphere inside capsule 140 wherethe hydrogen which is generated by the decomposition of water vapor isdone so at a rate that is equal to or greater than the rate of hydrogenpermeation through the refractory metal walls of components 115, 120,122, 125, 127 and 130 that would be occurring if an ambient atmospherewas present at the non-glass contact surface of the components.

Although the foregoing exemplary control system was described in termsof supplying hydrogen to the capsule volume via the breakdown of watervapor, and thus included a variety of controls and piping necessary toaccomplish this goal, the system could be easily modified to supply drygases, including a hydrogen containing gas, in order to directly controlthe hydrogen partial pressure within the capsule volume without undueexperimentation.

While the generation rate of neutral oxygen gas at the refractorymetal-glass melt interface is proportional to the hydrogen permeationrate, analysis of actual glass production data shows that blisterformation is also sensitively dependent upon the absolute concentrationof reduced multivalent compounds, such as SnO and As₂O₃, in the melt,and the amount of water in the glass. It will be understood throughoutthis description that water, as used herein, is used to denote bothmolecular water (H₂O) and the hydroxyl ion (OH). Cations of theaforementioned reduced multivalent species are capable of reacting withneutral oxygen gas and converting it to dissolved oxide complexes of ahigher valence state, e.g. SnO₂ and As₂O₅. Here, the term multivalentcations refers to ionized forms of a multivalent element, such as, butnot limited to, iron (Fe²⁺ or Fe³⁺), arsenic (As³⁺ or As⁵⁺), antimony(Sb³⁺ or Sb⁵⁺) and tin (Sn²⁺ or Sn⁴⁺). The concentration of water ismost conveniently determined by the cross section of the O—H fundamentalstretching mode at approximately 3600 cm¹ as measured by IR spectroscopyand expressed as β_(OH) in mm⁻¹. The presence of reduced multivalentcompounds in the glass counteracts at least part of the tendency ofhydrogen permeation to form blisters. When the concentration of reducedmultivalent compounds is high, or when the concentration of water in theglass melt is low (low β_(OH)), then the pH₂ required in the atmosphereoutside the refractory metal vessel to suppress gaseous inclusions iscomparatively low. However, when the concentration of reducedmultivalent compounds is low or β_(OH) is high, the pH₂ required tosuppress gaseous inclusions is comparatively high. As used herein, pH₂denotes the partial pressure of hydrogen, and in particular, the partialpressure of hydrogen in contact with the non-glass contact surface(s) ofthe refractory metal vessel containing the molten glass.

For certain environmentally-friendly glasses, so called “green” glasses,such as those glasses which might be used in the manufacture of glassfor flat panel display applications, the total concentration ofmultivalent cations in the glass is intentionally maintained at lowlevels. For example, in display applications antimony and arsenic istypically maintained at or below 0.05 wt. % (0.016 mole % As₂O₃ and0.011 Sb₂O₃) in order to qualify as “green”. Iron is preferablymaintained at or below 0.08 wt. % (0.033 mole %) to ensure adequatetransparency of the glass sheet. Tin is preferably at a low level toavoid precipitation of tin oxide (e.g. cassiterite) during the formingprocess as the molten glass is being drawn into a glass sheet. At thesame time, melting tank sizes are being increased, with increased freesurface areas, and the use of gas oxygen burners to melt the batchmaterials into molten glass, to address increasing production demands,have contributed to higher water levels in the molten glass. The resultmay be the generation of glass with β_(OH) levels in excess of 0.35mm⁻¹, and typically greater than about 0.4 mm⁻¹ or in some embodimentsgreater than about 0.5 mm⁻¹. While the addition of chlorine to the batchhas been taught as a method of reducing water levels in the moltenglass, in practice the high chlorine concentration effluent which isgenerated in such an approach proves to be a serious pollution abatementchallenge that adds considerably to production costs.

It can be appreciated that, due not in small part to environmental andcost concerns, the chemical barriers to blister formation have beenlargely eliminated from the glass composition, such chemical barriersnow being limited to tramp amounts of arsenic and antimony resultingfrom contaminants in the batch materials themselves, and low levels ofiron and tin. At the same time factors involved in increased productiondemands have contributed to an increase in the overall water content ofthe glass melt. Thus, a glass making process which incorporatesinterfaces between the molten glass and a refractory metal may require asignificant partial pressure of hydrogen outside the refractory metalvessel to successfully form the glass without gaseous inclusions.

We have found that it is possible to describe the relative impact of thethree process variables that largely control hydrogen permeation in asingle mathematical expression, making it possible to provide apermeation or “blister index” I_(b). The three process variables, fromthe preceding description, are the water content, β_(OH) , the partialpressure of hydrogen pH₂ in the atmosphere in contact with an outsidesurface of the refractory metal vessel or vessels, and the totalconcentration of reduced multivalent oxide compounds present in themelt, where the concentrations are denoted by brackets, e.g. [SnO]. Theblister index may be calculated for a specific location on therefractory metal system as:I_(b)=Δ√{square root over (pH₂)}−KΣ([SnO],[As₂O₃],[Sb₂O₃],[FeO],etc.)  (1)where K is a constant.

For an actual refractory metal-containing glass manufacturing system,Equation (1) can be expressed as:I_(b)=(√{square root over (p_(H) ₂ _(,in))}−√{square root over (p_(H) ₂_(,out))})−KΣα_(i)[M_(i) ^(b) ₁ ⁺]  (2)where p_(H) ₂ _(,in) is the H₂ partial pressure in the melt (whichdepends on [OH] through the equation p_(H2,in) =k[OH]², where thecoefficient k must be determined experimentally for each glasscomposition), p_(H) ₂ _(,out) is the H₂ partial pressure in contact withthe non-glass contacting side of the refractory metal, Σα_(i)[M_(i) ^(b)₁ ⁺] is the equivalent molar concentration of reduced multivalent oxidecompounds capable of absorbing O₂, K is a constant that must bedetermined experimentally and which accounts for process conditions, thedesign of the glass making system, the base glass composition, etc.Looking back to Equation (2) again, by running multiple experiments withrespect to a given point in the refractory metal portion of the glassmaking system, one can solve for K and I_(b).

As indicated by Equation (2), the blister index I_(b) consists of twoterms and depends on the three process variables that control blisterformation via hydrogen permeation. The first term, (√{square root over(p_(H) ₂ _(,in))}−√{square root over (p_(H) ₂ _(,out))}), describes O₂generation on the refractory metal due to hydrogen permeation, while thesecond term, KΣα_(i)[M_(i)], describes O₂ absorption by reducedmultivalent oxides, M_(i). The a_(i) coefficients are the number ofmoles of O₂ that can be absorbed by one mole of the reduced multivalentoxide. As can be seen, Equation (2) represents a relationship betweenoxygen generation and oxygen depletion.

A critical value of I_(b) (I_(bc)) serves as a demarcation betweenacceptable and unacceptable blister production, the acceptable level ofblisters being dependent upon the intended application for the glass,customer requirements, etc. I_(bc) is determined for a specific glassmelting unit and blister source location from a correlation of blisterlevel and blister index over a range of one or more of the three processvariables described supra. The blister concentration for each set ofconditions is determined by counting the number of detectable blistersper pound of finished (e.g. drawn) glass. The number of blisters perpound of glass is then plotted against I_(b) as illustrated in FIG. 2,and a critical value of I_(b) determined by drawing a line at theacceptable blister level (a horizontal line if blisters per pound ofglass is plotted on the vertical y-axis). I_(bc) may then be obtainedfrom the plot by noting the intercept point of the correlation curve 10(e.g. a best-fit curve to the plotted data) with the acceptable blisterlevel. For example, in the illustrative plot shown in FIG. 2, theacceptable blister level is assumed to be zero detectable blisters perpound of glass, i.e. the x-axis in the figure. Therefore I_(bc) is thevalue of I_(b) at the x-axis intercept. In a practical glass makingprocess the number of blisters should be maintained at least equal to orless than about 0.2 blisters per pound of glass, and preferably equal toor less than about 0.02 blisters per pound of glass.

Since blister formation depends on the net O₂ production rate at therefractory metal-glass melt interface, the blister index describedherein (which accounts for both O₂ generation and O₂ absorption) willpredict blister formation better than hydrogen permeation rate alone(which accounts only for O₂ generation). The key is capturing thereduction-oxidation state (redox state) of the melt, i.e. the O₂absorption capacity of the reduced multivalent ions.

Once the critical value of I_(b) is known, it is possible to predict theconditions required to produce blister-free glass. Of particular utilityis the ability to translate an undesirable change in one processvariable to a required change in another process variable to maintainblister-free glass. For example, the I_(bc) can be used to determine theincrease in the imposed external pH₂ required to offset a decrease inthe concentration of reduced SnO in the melt. Or, the sand or sandscomprising the batch material may be changed (some sands are “drier”than other sands) to control the water content of the glass melt.Alternatively, the method of heating and melting the glass melt may bemodified, such as using a gas-air burner as opposed to a gas-oxygenburner. If the source of sand is fixed and the partial pressure is nolonger controllable, the multivalent oxide compound content of the glassmelt may be modified, for example, by adjusting the amount ofmultivalent oxide compound (e.g. arsenic oxide, antimony oxide, tinoxide, etc.) added to the initial batch materials. Preferably, themultivalent compound(s) introduced into the batch material results in afinished glass article comprising a total tin content expressed as SnO₂that is less than or equal to about 0.112 mole %, a total arseniccontent expressed as As₂O₃ that is less than or equal to about 0.016mole %, a total antimony content expressed as Sb₂O₃ that is less than orequal to 0.011 mole %, and a total iron content expressed as Fe₂O₃ thatis less than or equal to about 0.037 wt. %. However, hydrogen partialpressure is the variable most likely to be controlled, as it representsthe most manageable attribute, both in terms of ease of adjustment, andwith respect to the speed of impact on blister production.

While the foregoing provides a useful method for the design of a newglass making system, or for setting the process set points for aspecific existing system, the previous discussion may be extended suchthat for a glass that is substantially free of alkalis, arsenic, andantimony, and that includes an interface with a refractory metal at atemperature greater than or equal to about 1550° C., the exterior of therefractory metal vessel must be enclosed in an atmosphere comprising apartial pressure of hydrogen above a predetermined minimum tosuccessfully form glass which is essentially free of gaseous inclusions.

More fundamentally, the generation and consumption of oxygen within theglass melt may be modeled, and from that modeling the minimum partialpressure of hydrogen in the atmosphere surrounding the refractory metalvessel(s) of the glass making system can be expressed as a function ofβ_(OH) according to the following equation:pH₂=2.39×10⁻⁴*β_(OH) ²−1.81×10⁻⁴*β_(OH)+3.52×10⁻⁵ bars  (3)where pH₂ is the minimum partial pressure of hydrogen in the atmospheresurrounding the refractory metal vessel (e.g. within capsule 140) toachieve a gaseous inclusion level of less than or equal to 0.2inclusions per pound of glass, and β_(OH) is as previously defined.Equation (3) is plotted in FIG. 3 for a hypothetical glass compositionat a temperature of 1550° C. which is essentially free of arsenic andantimony (a total arsenic concentration expressed as As₂O₃ less than orequal to 0.016 mole % and a total antimony concentration expressed asSb₂O₃ less than or equal to about 0.011 mole %) and a β_(OH) in theglass melt greater than or equal to about 0.4 mm⁻¹, but which may begreater than about 0.5 mm⁻¹. Additionally, the glass composition assumedfor the plot of FIG. 3 is assumed to contain a total tin concentrationexpressed as SnO₂ of less than about 0.112 mole % and a total ironconcentration expressed as Fe₂O₃ of less than or equal to about 0.033mole %. The refractory metal thickness of the vessel containing themolten glass is assumed to be less than or equal to about 1 mm. Thethickness of the refractory metal vessel wall is selected as less thanor equal to 1 mm for practical reasons: while a thicker refractory metalwall would serve to decrease the hydrogen permeation rate, there is apoint at which it becomes prohibitively expensive to manufacture largerefractory vessels with thick walls, given that the majority of therefractory metals contain, or are primarily composed of expensiveprecious metals. Conversely, the wall thickness should be selected to bethick enough that the vessel is capable of supporting itself. The curvedisplayed in FIG. 3 then represents the critical value of pH₂ tosuppress blister production. The above assumptions represent aconservative estimate for pH₂. That is, process variations serve toincrease the pH₂ necessary in the atmosphere in contact with thenon-glass contact surface of the refractory metal vessel. For example,for temperatures greater than 1550° C., the pH₂ necessary in theatmosphere in contact with the non-glass contact surface of therefractory metal vessel in order to suppress blisters also increases. Ifthe concentration of reduced multivalent compounds decreases below theupper limit, the pH₂ which is necessary in the atmosphere in contactwith the non-glass contact surface of the refractory metal vessel tosuppress blister increases. Similarly, if the β_(OH) of the glassincreases, the pH₂ necessary in the atmosphere in contact with thenon-glass contact surface of the refractory metal vessel in order tosuppress blister increases.

In one embodiment, the glass article produced according to the presentinvention comprises a total tin content expressed as SnO₂ that is lessthan or equal to about 0.112 mole. %, a total arsenic content expressedas As₂O₃ that is less than or equal to about 0.016 mole %, a totalantimony content expressed as Sb₂O₃ that is less than or equal to 0.011mole % and a total iron content expressed as Fe₂O₃ that is less than orequal to about 0.037 mole %.

In accordance with FIG. 3, for a given β_(OH) in the molten glass, aminimum pH₂ for the atmosphere surrounding the non-glass contact surfaceof the refractory metal vessel can be easily determined from the plottedcurve. That is, as long as one maintains the pH₂ surrounding arefractory metal vessel above and to the left of the curve in FIG. 3,blister production in the molten glass can be suppressed, i.e.maintained less than about 0.2 bubbles (inclusions) per pound of glass,preferably below 0.02 inclusions per pound of glass.

The above explanation can be expanded further with the understandingthat one may consider not only the upper limits for arsenic, antimony,tin and iron, but all multivalent species, and instead specify a maximumlimit for the total concentration of all multivalent species. In thisinstance it is appropriate to consider the total concentration ofreduced multivalent species.

The total concentration of reduced multivalent species can be determinedby summing the mole percent of each reduced multivalent compound,wherein each mole % is multiplied by the number of molecules of O₂absorbed by the particular compound, to wit, the total molarconcentration of the reduced multivalent compounds=1*(mole %As₂O₃)+1*(mole % Sb₂O₃)+0.5*(mole % SnO +0.25*(mole % FeO)+0.5*(mole %CeO₂)+. . . . More generically, the preceding equation may be written asTotal Reduced Multivalent Compounds=Σ(n_(i)[M_(i)]) between 1 and i,where i represents the number of reduced multivalent species present inthe glass, [M_(i)] represents the concentration of the i^(th) reducedmultivalent compound, and n_(i) represents the number of molecules of O₂absorbed when one mole of the i^(th) reduced multivalent compound isoxidized.

A more practical method of determining the total reduced multivalentconcentration can be determined from(W_(glass))*Σ_(i)([P_(i)]/W_(i)*U_(i)) where W_(glass) is the averagemolecular weight of the glass in units of g/mole, n_(i) is as previouslydefined, [P_(i)] is the total concentration of the i^(th) multivalentcompound in wt. %, U is the mole fraction of the i^(th) multivalentcompound in the reduced state and W_(i) is the total molecular weight ing/mole of the i^(th) multivalent compound. The summation is performedbetween the ranges of 1 and i, where again i represents the number ofmultivalent compounds present in the glass. U can be determined as(X_(r)/X_(r)+X_(o)) where X_(r) is the molar concentration of the i^(th)reduced multivalent compound, and X_(o) is the molar concentration ofthe i^(th) oxidized multivalent compound.

In a practical glass making system it is difficult if not impossible todetermine the actual concentration of reduced or oxidized multivalentcompounds in the 1550° C. molten glass, or the β_(OH) of the moltenglass. Thus, for a practical glass making system in accordance with theforegoing discussion, Equation (3) and FIG. 3 may be interpreted in thefollowing manner: for a glass article formed from a molten glassprocessed in a refractory metal vessel or vessels at a temperature inexcess of 1550° C., and wherein the glass of the glass article comprisesa β_(OH) greater than or equal to about 0.4 mm⁻¹, and the glass of theglass article further comprises a total reduced multivalentconcentration of less than or equal to 0.04 mole %, the minimum pH₂ incontact with the non-glass-contacting surface of the refractory metalvessel (e.g. fining tube 115) should be greater than about 10⁻⁶ bar.Under these conditions, the glass of the glass article may be formedcomprising no more than about 0.2 bubbles (inclusions) per pound ofglass. It should be noted that if the total multivalent concentration ofthe glass is considered, as opposed to just the reduced species (e.g.SnO, FeO, As₂O₃, Sb₂O₃, CeO₂, etc.) the limit on multivalentconcentration in the formed glass will be greater than 0.04 mole %. Itshould also be appreciated that the concentration of reduced multivalentcompounds in the formed glass article is substantially the same as theconcentration of reduced multivalent compounds in the molten glass. Thisoccurs for the following reason: As the multivalent compound is heatedin the molten glass, the compound is reduced and releases oxygen. If thereduction takes place in fining (conditioning) tube 115, for example,the oxygen, which joined a bubble, travels to a free surface of themolten glass and is eliminated from the molten glass. As the moltenglass continues through the refractory metal system (beyond the finingvessel), the glass, and the multivalent compound, cool. Although in thepresence of free oxygen the multivalent compound would oxidize,substantially all of the free oxygen was previously eliminated, and thecompound remains in a reduced state. In practice, the concentration ofwater, expressed through β_(OH), also does not change appreciably duringprocessing of the glass within the refractory metal system and thereforemay be measured in the resultant glass article and be representative ofthe β_(OH) concentration in the molten glass during its transit in therefractory metal system, and in particular, after conditioning in thefining vessel.

In practice, many tanks for melting the batch materials in themanufacture of glass are electrically heated, and comprise tinelectrodes. The electrodes slowly dissolve, leading to higher tinconcentrations in the melt. The foregoing limits on multivalentcompounds (as opposed to reduced multivalent compounds) may be modifiedto accommodate higher tin levels such that a maximum tin concentration(i.e. the sum of both the reduced and oxidized species, SnO and SnO₂,respectively), may be established between 0.01 mole % and 0.112 mole %.The maximum concentration of all other multivalent compound, that is allother non-tin containing multivalent compounds, may nevertheless bemaintained at less than or equal to about 0.04 mole %.

It should be emphasized that the above-described embodiments of thepresent invention, particularly any “preferred” embodiments, are merelypossible examples of implementations, merely set forth for a clearunderstanding of the principles of the invention. Many variations andmodifications may be made to the above-described embodiments of theinvention without departing substantially from the spirit and principlesof the invention. All such modifications and variations are intended tobe included herein within the scope of this disclosure and the presentinvention and protected by the following claims.

1. A method of making a glass article comprising: flowing a molten glassat a temperature of at least about 1550° C. in a vessel comprising arefractory metal wall having an inside surface in contact with themolten glass, and wherein a partial pressure of hydrogen at an outsidesurface of the refractory metal wall is at least about 10⁻⁶ bar; formingthe molten glass into the glass article; and wherein the glass articlecomprises a total concentration of reduced multivalent compounds equalto or less than about 0.04 mole %, a β_(OH) of at least about 0.4 mm⁻¹and no more than 0.2 gaseous inclusions per pound of glass.
 2. Themethod according to claim 1 wherein the glass article further comprisesa total concentration of SnO₂ and SnO less than or equal to 0.112 mole%.
 3. The method according to claim 1 wherein the total concentration ofSnO₂ and SnO is between 0.01 and 0.112 mole %
 4. The method according toclaim 1 wherein the glass article is essentially free of alkali.
 5. Themethod according to claim 1 wherein the glass article comprises: a totaltin content expressed as SnO₂ that is less than or equal to about 0.112mole %; a total arsenic content expressed as As₂O₃ that is less than orequal to about 0.016 mole %; a total antimony content expressed as Sb₂O₃that is less than or equal to 0.011 mole %; and a total iron contentexpressed as Fe₂O₃ that is less than or equal to about 0.037 mole %. 6.The method according to claim 1 wherein the glass article furthercomprises no more than about 0.02 gaseous inclusions per pound of glass.7. The method according to claim 1 wherein the glass article is a glassribbon suitable for use in producing glass substrates for displayapplications.
 8. The method according to claim 1 wherein a thickness ofthe refractory metal wall is no greater than about 1 mm.
 9. The methodaccording to claim 1 wherein the refractory metal wall comprises a metalselected from the group consisting of iridium, osmium, palladium,platinum, rhodium, ruthenium, molybdenum, tin, antimony, silver, gold,iron and alloys thereof.
 10. A method of making a glass articlecomprising: flowing a molten glass at a temperature of at least about1550° C. in a vessel comprising a refractory metal wall having an insidesurface in contact with the molten glass, and wherein a partial pressureof hydrogen at an outside surface of the refractory metal wall is atleast about 10⁻⁶ bar; forming the molten glass into the glass article;and wherein the glass article comprises a β_(OH) of at least about 0.4mm⁻¹, a total concentration of SnO and SnO₂ less than or equal to 0.112mole %, a total concentration in the glass article of all othermultivalent compounds not comprising tin is less than or equal to about0.04 mole % and no more than 0.2 gaseous inclusions per pound of glass.11. The method according to claim 10 wherein the refractory metal wallcomprises a metal selected from the group consisting of iridium, osmium,palladium, platinum, rhodium, ruthenium, molybdenum, tin, antimony,silver, gold, iron and alloys thereof.
 12. The method according to claim10 wherein the glass article comprises no more than about 0.02 gaseousinclusions per pound of glass.
 13. A glass article made by the processaccording to claim
 10. 14. The method according to claim 10 wherein theglass article is a glass ribbon suitable for use in producing glasssubstrates for display applications.
 15. The method according to claim10 wherein the glass article further comprises: a total arsenic contentexpressed as As₂O₃ that is less than or equal to about 0.016 mole %; atotal antimony content expressed as Sb₂O₃ that is less than or equal to0.011 mole %; and a total iron content expressed as Fe₂O₃ that is lessthan or equal to about 0.037 mole %.
 16. A method of making a glassarticle comprising: flowing a molten glass at a temperature of at leastabout 1550° C. in a vessel comprising a refractory metal wall having aninside surface in contact with the molten glass, and wherein a partialpressure of hydrogen (pH₂) in bar at an outside surface of therefractory metal wall is greater than or equal to an amount calculatedaccording to the expression pH₂=2.39×10⁻⁴β_(OH)²−1.81×10⁻⁴β_(OH)+3.52×10⁻⁵ bar; forming the molten glass into the glassarticle; and wherein the glass article comprises a β_(OH) of at leastabout 0.4 mm⁻¹, a total of no more than about 0.04 mole % of reducedmultivalent compounds and no more than 0.2 gaseous inclusions per poundof glass.
 17. The method according to claim 16 wherein the glass articleis a glass substrate suitable for use in display applications.
 18. Themethod according to claim 16 wherein the glass article comprises: atotal tin content expressed as SnO₂ that is less than or equal to about0.112 mole %; a total arsenic content expressed as As₂O₃ that is lessthan or equal to about 0.016 mole %; a total antimony content expressedas Sb₂O₃ that is less than or equal to 0.011 mole %; and a total ironcontent expressed as Fe₂O₃ that is less than or equal to about 0.037mole %.
 19. A glass sheet comprising; a total tin content expressed asSnO₂ that is less than or equal to about 0.112 mole %; a total arseniccontent expressed as As₂O₃ that is less than or equal to about 0.016mole %; a total antimony content expressed as Sb₂O₃ that is less than orequal to 0.011 mole %; a total iron content expressed as Fe₂O₃ that isless than or equal to about 0.037 mole %; and wherein the glass sheetcontains no more than 0.2 gaseous inclusions per pound of glass.
 20. Amethod of making a glass article comprising: melting a batch materialcomprising a multivalent compound to form a glass melt; flowing theglass melt through a refractory metal vessel, an atmosphere in contactwith an outside surface of the refractory metal vessel comprising apartial pressure of hydrogen pH₂; forming a glass article from the glassmelt, the glass article comprising a concentration of a reducedmultivalent oxide compound and a water content expressed as β_(OH);calculating a blister index from the reduced multivalent oxide compoundconcentration, the β_(OH) concentration and the partial pressure ofhydrogen; and maintaining the blister index below a predetermined valueby controlling the multivalent oxide compound in the batch material, thewater content, and the partial pressure of hydrogen, or a combinationthereof.
 21. The method according to claim 20 wherein the partialpressure of hydrogen is controlled by controlling an effective dew pointof the atmosphere.
 22. The method according to claim 20 wherein thepartial pressure of hydrogen is controlled by varying a concentration ofa hydrogen containing gas in the atmosphere.
 23. The method according toclaim 20 wherein the glass melt is essentially free of arsenic orantimony.
 24. The method according to claim 20 wherein the multivalentoxide compound comprises tin.
 25. The method according to claim 20wherein the glass article comprises: a total tin content expressed asSnO₂ that is less than or equal to about 0.112 mole %; a total arseniccontent expressed as As₂O₃ that is less than or equal to about 0.016mole %; a total antimony content expressed as Sb₂O₃ that is less than orequal to 0.011 mole %; a total iron content expressed as Fe₂O₃ that isless than or equal to about 0.037 mole %.
 26. The method according toclaim 20 wherein the glass article comprises no more than about 0.2gaseous inclusions per pound of glass.
 27. The method according to claim20 wherein the glass article comprises no more than about 0.02 gaseousinclusions per pound of glass.
 28. A method of making a glasscomprising: flowing a molten glass at a temperature of at least about1550° C. in a vessel comprising a platinum or platinum alloy wall havingan inside surface in contact with the molten glass, and wherein apartial pressure of hydrogen at an outside surface of the platinum orplatinum alloy wall is at least about 10⁻⁶ bar; and wherein theresultant glass comprises a total concentration of reduced multivalentcompounds equal to or less than about 0.04 mole %, a β_(OH) of at leastabout 0.4 mm⁻¹ and no more than 0.2 gaseous inclusions per pound ofglass.
 29. The method according to claim 28 wherein the β_(OH) is atleast about 0.5 mm⁻¹.